Correlation of vibrational intensity with fluorescence lifetimes in π conjugated polymers |
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Authors: | Luke O'Neill Patrick Lynch Mary McNamara Hugh J Byrne |
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Affiliation: | a School of Physics, Dublin Institute of Technology, Kevin Street, Dublin 8, Ireland b School of Chemical and Pharmaceutical Sciences, Dublin Institute of Technology, Kevin Street, Dublin 8, Ireland c Focas Research Institute, Dublin Institute of Technology, Camden Row, Dublin 8, Ireland |
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Abstract: | A series of novel pi (π) conjugated polymers, originating from the archetypical Polyphenylene vinylene, in which the phenyl units are successively replaced by the larger naphthyl and anthryl acene units, were previously found to have a well-defined relationship between their relative fluorescence yields and their vibrational characteristics, as determined by Raman spectroscopy. In this study the Strickler-Berg equation is used to probe the influence of continual substitution of higher order acene units into the conjugated backbone in terms of the variation of the radiative and non-radiative rates. The deconvolution of the radiative and non-radiative rates enables the correlation of the reduction of the Raman intensity and concomitant increase in the fluorescence yield with the reduction of the non-radiative rate. This confirms that the reduction of the non-radiative rate is the dominant process introduced by the vibrational confinement originating from systematic substitution of higher order acene units into the polymer backbone. |
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Keywords: | Polymers Raman spectroscopy Fluorescence lifetimes |
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